Process for the preparation of nitroanilines

ABSTRACT

The invention relates to a process for the preparation of nitroanilines, which consists in reacting an amine RNH 2 , or ammonia, with 3,4-methylenedioxynitriobenzene to give the products of the formula: ##STR1## in which R denotes hydrogen, alkyl, monohydroxyalkyl or polyhydroxyalkyl, alkoxyalkyl or aminoalkyl of the formula: ##STR2## in which R 1  and R 2 , which are identical or different, denote hydrogen, alkyl or monohydroxyalkyl or polyhydroxyalkyl and n denotes an integer from 2 to 4, or of the formula: ##STR3## in which A denotes OCH 2  or ##STR4## and R 1  denotes --CH 2  CH 2  OH or ##STR5## or their salts. The invention also relates to the dyeing compositions for keratin fibres, and in particular for hair, which contain a dyestuff of the above formula (I) in which R denotes alkyl, polyhydroxyalkyl, alkoxyalkyl or aminoalkyl of the abovementioned formula, and to the dyestuffs of the formula (I) in which R denotes alkoxyalkyl or aminoalkyl of the above formula, and of the formula (IIB), which are novel.

This is a continuation of application Ser. No. 410,981 filed Aug. 24,1982, now abandoned.

The present invention relates to a new process for the preparation ofnitroanilines, to the use of these nitroanilines in dyeing compositionsfor keratin fibres, and in particular for human hair, and to the newnitroanilines prepared by this process.

The present invention relates more particularly to a process for thepreparation of compounds of the general formula: ##STR6## in which Rdenotes hydrogen, alkyl, alkyl substituted by one or more OH groups,alkoxyalkyl, or aminoalkyl of the formula: ##STR7## in which R₁ and R₂can be identical or different and denote hydrogen, alkyl or alkylsubstituted by one or more OH groups, and their salts

A certain number of processes are already known which make it possibleto prepare compounds belonging to this family of nitroanilines, forexample the process described by Bower and Stephens, JCS, 1951, page325, or in British Patent No. 1 168 105. These processes consist instarting from benzoxazolone and generally comprise three steps.Furthermore, a process is described in British Patent No. 1 012 793which makes it possible to prepare2-N-(β-hydroxyethyl)-amino-5-nitrophenol, in particular, by reactingglycol chlorohydrin with 2-amino-5-nitrophenol in the presence ofanhydrous sodium acetate and iodine. However, this process has thedisadvantage of giving a relatively low yield and of giving rise to theformation of a mixture of compounds which must be separated.

The process according to the invention makes it possible to prepare thecompounds of the formula (I) with an improved yield by reacting an amineRNH₂, in which R has the meaning indicated above, with3,4-methylenedioxynitrobenzene. This process is particularly valuable byvirtue of the ease with which it can be carried out, since it involvesonly one step, and by virtue of the purity of the products which canthereby be obtained.

This process also makes it possible to prepare new compounds belongingto the family of the compounds of the formula (I), which are veryvaluable from the point of view of their use in hair dyeing. In fact,these compounds have the advantage of being very luminous directdyestuffs having a good resistance to adverse weather conditions andwashing, and also a good degree of harmlessness.

The process according to the present invention, which makes it possibleto prepare compounds corresponding to the formula: ##STR8## in which Rdenotes hydrogen, alkyl, monohydroxyalkyl or polyhydroxyalkyl,alkoxyalkyl, or aminoalkyl of the formula: ##STR9## in which R₁ and R₂,which are identical or different, denote hydrogen, alkyl ormonohydroxyalkyl or polyhydroxyalkyl and n denotes an integer from 2 to4, and their salts, is characterised in that an amine of the formulaRNH₂, in which R has the meaning indicated above, or ammonia, is reactedwith 3,4-methylenedioxynitrobenzene.

This process can essentially be summarised by the following equation:##STR10##

According to this process, 3,4-methylenedioxynitrobenzene is desirablyheated in an excess of amine of the formula RNH₂. The operatingconditions, such as temperature and reaction time, vary according to thenature of the amine used. The temperature is preferably from 70° to 170°C. and the reaction time is suitably 1 hour to 30 hours.

Once the reaction has ended, the excess amine RNH₂ can be removed invacuo. A virtually pure product can be obtained by carrying out thefollowing processes:

(a) In the case where R is an alkyl, monohydroxyalkyl orpolyhydroxyalkyl or alkoxyalkyl group, the crude reaction product, whichmay or may not still contain the amine RNH₂, is treated with a dilutesolution of hydrochloric acid. The product insoluble in the dilutehydrochloric acid medium is isolated, washed with water and then treatedwith a dilute solution of sodium hydroxide. The fraction insoluble inthe sodium hydroxide medium, which consists of the unreacted initialproduct, is removed by filtration. By acidification of the filtrate, theexpected product can be obtained virtually pure.

(b) In the case where R denotes the group ##STR11## the crude reactionproduct, which may or may not still contain the amine RNH₂, is taken upin a 2 to 3N solution of hydrochloric acid. After cooling, the expectedproduct crystallises in the form of the monohydrochloride. By washingthis hydrochloride with a solvent, traces of initial nitro derivativecan be removed, if necessary. The hydrochloride can be recrystallisedfrom water.

In the case where R denotes hydrogen, 3,4-methylenedioxynitrobenzene isdesirably heated, in an autoclave, in a mixture of ammonia and anon-alcoholic solvent, such as an alkylene glycol ether. Afterprecipitation of the unreacted initial product, filtration andneutralisation with hydrochloric acid, the acetyl derivative can beobtained, which, after acid hydrolysis and neutralisation of thereaction medium, leads to the desired product.

The compounds more particularly prepared according to the invention arethose in which R denotes an unsubstituted or hydroxy, alkoxy oramino-substituted alkyl group having 1 to 4 carbon atoms. Amongst thesegroups, there may be mentioned methyl, ethyl, propyl, n-butyl,β-hydroxyethyl, β-aminoethyl, diethylaminoethyl or β,α-dihydroxypropylgroup. The salts are preferably in the form of the hydrochloride,hydrobromide or sulphate.

We have also discovered that, by using, as the amine, an amine of theformula R₁ NH₂, in which R₁ denotes CH₂ CH₂ --OH or CH₂ CHOHCH₃, thereaction with 3,4-methylenedioxynitrobenzene leads to the formation oftwo compounds corresponding to the formulae: ##STR12## in which R₁ hasthe meaning indicated above and A denotes a group --O--CH₂ CH₂ -- or##STR13## this discovery constitutes a further aspect of the presentinvention.

This process is essentially characterised in that an amine of theformula R₁ NH₂, in which R₁ denotes a group --CH₂ CH₂ OH or --CH₂CHOHCH₃, is reacted with 3,4-methylenedioxynitrobenzene by heating3,4-methylenedioxynitrobenzene in an excess of amine of the formula R₁NH₂, at a temperature of, say, 70° to 170° C., for, say, 1 to 30 hours,in that a dilute solution of hydrochloric acid is added to the crudereaction product obtained, in that the product insoluble in thehydrochloric acid medium is filtered off, in that it is purified to givea compound of the formula: ##STR14## in that the mother liquors fromfiltration are rendered alkaline with a solution of sodium hydroxide, inthat the product which precipitates in the sodium hydroxide medium isisolated and purified, the said product corresponding to the formula:##STR15##

In the process described above, the product insoluble in the dilutehydrochloric acid medium can be separated off and washed and thentreated with a dilute solution of sodium hydroxide. The fractioninsoluble in the sodium hydroxide medium, which consists of theunreacted initial product, can then be removed by filtration. Byacidification of the filtrate, the product of the formula (IIA) can beobtained virtually pure.

The product precipitated from the mother liquors arising fromfiltration, which have been rendered alkaline, can be obtained after themother liquors have first been cooled to 0° C. The precipitate isfiltered off, washed with water and dried.

The preferred new compounds prepared according to this processcorrespond to the following formulae: ##STR16##

These compounds can also be prepared in the form of their salts, such asthe hydrochloride, hydrobromide or sulphate.

The compounds prepared according to the invention are particularlysuitable for use in dyeing compositions for keratin fibres, inparticular for human hair.

The dyeing compositions for keratin fibres, and in particular for humanhair, according to the present invention are essentially characterisedin that they contain at least one dyestuff corresponding to the formula:##STR17## in which R' denotes an alkyl group, a group ##STR18## apolyhydroxyalkyl group, an alkoxyalkyl group or an aminoalkyl group ofthe formula: ##STR19## in which R₁ and R₂, which are identical ordifferent, denote hydrogen, alkyl or monohydroxyalkyl orpolyhydroxyalkyl and n is an integer from 2 to 4, or of the formula:##STR20## in which R₁ denotes the group --CH₂ CH₂ OH or --CH₂--CHOH--CH₃ and A denotes the group --OCH₂ CH₂ -- or ##STR21## ormixtures thereof, or a cosmetically acceptable salt of these compounds.

These compositions according to the invention, which contain at leastone compound corresponding to the formula (III) or (IIB), in acosmetically acceptable solvent medium, can be used for the directdyeing of keratin fibres or in the oxidation dyeing of these fibres, inwhich case the compounds of the formula (III) or (IIB) impart acomplementary sheen to the base coloration obtained by oxidativedevelopment of oxidation dyestuff precursors.

These compositions suitably contain the compound of formula (III) or(IIB) in an amount from 0.001 to 5% by weight, and preferably 0.01 to 3%by weight, relative to the total weight of the dyeing composition.

They can contain anionic, cationic, non-ionic or amphotericsurface-active agents or mixtures thereof, and preferably cationicand/or non-ionic surface-active agents. These surface-active productsare suitably present in the compositions of the invention in an amountfrom 0.5 to 55% by weight, and preferably 2 to 40% by weight, relativeto the total weight of the composition.

In cosmetic application, the cosmetic vehicle generally consists ofwater; organic solvents can also be included in the compositions inorder to solubilise compounds which would not be sufficiently soluble inwater. Amongst these solvents, there may be mentioned lower alkanols(i.e. of 1 to 6, especially 1 to 4, carbon atoms), such as ethanol andisopropanol, polyols, such as glycerol, glycols or glycol ethers, suchas 2-butoxyethanol, ethylene glycol, ethylene glycol monoethyl ether,propylene glycol, and diethylene glycol monoethyl ether and monomethylether, and mixtures thereof. These solvents are preferably present inamounts from 1 to 75% by weight, and in particular from 5 to 50% byweight, relative to the total weight of the composition.

The compositions can be thickened, preferably with sodium alginate, gumarabic, cellulose derivatives, such as methylcellulose,hydroxyethylcellulose, hydroxypropylmethylcellulose andcarboxymethylcellulose, and various polymers acting as thickeners, moreparticularly acrylic acid derivatives It is also possible to useinorganic thickeners, such as bentonite. These thickeners are preferablypresent in amounts of 0.5 to 10% by weight, and in particular 0.5 to 3%by weight, relative to the total weight of the composition.

The compositions according to the invention can also contain variousadjuvants normally used in hair-dyeing sequestering agents, film-formingagents, buffers, perfumes, alkalising agents and acidifying agents.

These compositions can be presented in various forms, such as a liquid,cream or gel or any other form suitable for hair dyeing. Further, theycan be packaged in aerosol cans in the presence of a propellant.

The pH of these dyeing compositions is suitably 3 to 11.5 and preferably5 to 10.5. It is adjusted to the desired value with an alkalising agent,such as ammonia, sodium carbonate, potassium carbonate or ammoniumcarbonate, sodium hydroxide or potassium hydroxide, alkanolamines, suchas mono-, di- or tri-ethanolamine, 2-amino-2-methylpropanol or2-amino-2-methylpropane-1,3-diol, or alkylamines, such as ethylamine,diethylamine or triethylamine, or with an acidifying agent, such asphosphoric, hydrochloric, tartaric, acetic, lactic or citric acid.

If the compositions are intended for use in a process of direct dyeingof the hair, they can contain, in addition to the compounds according tothe invention, other direct dyestuffs, such as azo dyestuffs,anthraquinone dyestuffs, for example tetraminoanthraquinone,aminoquinones, nitrobenzene dyestuffs other than those of formula (III)or (IIB), and, more particularly, the following compounds:2-methyl-6-nitroaniline, 3-nitro-4-aminophenol,3-nitro-4-N-(β-hydroxyethyl)-aminophenol,3-nitro-4-amino-6-methylphenol, 3-amino-4-nitrophenol,2-amino-3-nitrophenol, 2-amino-5-nitrophenol,2-(β-hydroxyethyl)-amino-5-nitrophenol,3-nitro-6-N-(β-hydroxythyl)-aminoanisole,3-N-(β,γ-dihydroxypropyl)-amino-4-nitroanisole,3-N-methylamino-4-nitrophenoxyethanol,3-N-methylamino-4-nitrophenyl-β,γ-dihydroxypropyl ether,N,N'-di-(β-hydroxyethyl)-nitro-para-phenylenediamine and3-nitro-4-N'-methylamino-N,N-(di-β-hydroxyethyl)-aniline. Theconcentration of these direct dyestuffs other than the dyestuffs of theformula (III) or (IIB) is suitably 0.001 to 5% by weight, relative tothe total weight of the composition.

These compositions are applied to the keratin fibres for, say, 5 to 70minutes and the fibres are then rinsed, optionally washed and rinsedagain, and dried.

The compositions can be also be used in the form of hair-setting lotionsintended both for imparting a slight coloration to the hair and forimproving its hold. In this case, they are generally presented in theform of aqueous, alcoholic or aqueous-alcoholic solutions containing atleast one cosmetic resin, and they are applied to wet hair which hasbeen washed and rinsed beforehand, which is optionally wound ontorollers and then dried.

The cosmetic resins used in the setting lotions can be, in particular,polyvinylpyrrolidone, crotonic acid/vinyl acetate andvinylpyrrolidone/vinyl acetate copolymers, monoesters of maleicanhydride/butyl vinyl ether and maleic anhydride/methyl vinyl ethercopolymers, as well as other cationic, anionic, non-ionic or amphotericpolymers normally used in this type of composition. These cosmeticresins are generally present in the compositions of the invention inamounts of 1 to 3% by weight, and preferably of 1 to 2% by weight, basedon the total weight of the composition.

If the compositions constitute oxidation dye formulations, the compoundsof the formula (III) or (IIB) are used essentially in order to impart asheen to the final dyeing.

These compositions then contain oxidation dyestuff precursors inassociation with at least one nitro dyestuff of the formula (III) or(IIB).

They can contain, for example, para-phenylenediamines, such as:para-phenylenediamine, para-toluylenediamine,2,6-dimethyl-para-phenylenediamine,2,6-dimethyl-3-methoxypara-phenylenediamine,N-(β-methoxyethyl)-para-phenylenediamine,4-N,N-di-(β-hydroxyethyl)-aminoaniline,4-(N-ethyl-N-carbamylmethyl)-aminoaniline and also their salts.

They can also contain para-aminophenols, such as: para-aminophenol,N-methyl-para-aminophenol, 2-chloro-4-aminophenol,3-chloro-4-aminophenol, 2-methyl-4-aminophenol and their salts.

They can also contain heterocyclic derivatives, for example:2,5-diaminopyridine and 7-aminobenzomorpholine.

The compositions according to the invention can contain couplers whichare well known in the state of the art, in association with oxidationdyestuff precursors.

Couplers which may be mentioned in particular are: meta-diphenols, suchas resorcinol and 2-methylresorcinol, meta-aminophenols such as:meta-aminophenol, 2-methyl-5-aminophenol,2-methyl-5-N-(β-hydroxyethyl)-aminophenol and 6-hydroxybenzomorpholineand their salts, ethanol, 2,4-diaminophenyl β-hydroxypropyl ether,6-aminobenzomorpholine,2-N-(β-hydroxyethyl)-amino-4-aminophenoxyethanol, 2,4-diaminophenylβ,γ-dihydroxypropyl ether and their salts, and meta-acylaminophenols,metaureidophenols and meta-carbalkoxyaminophenols, such as:2-methyl-5-acetylaminophenol, 2-methyl-5-ureidophenol and2-methyl-5-carbethoxyaminophenol.

Finally, the following may be mentioned as other couplers which can beused in the compositions of the invention: α-naphthol, couplerspossessing an active methylene group, such as diketone compounds andpyrazolones, and heterocyclic couplers, such as 2,4-diamino-pyridine,and also their salts.

In addition to the oxidation dyestuff precursors, these compositions maycontain reducing agents, such as sodium sulphite, thioglycolic acid,thiolactic acid, sodium bisulphite, ascorbic acid and hydroquinone.These reducing agents are suitably present in amounts of 0.05 to 1.5% byweight, relative to the total weight of the composition. The oxidationdyestuff precursors are suitably present in the compositions of theinvention at concentrations of 0.001 to 5% by weight, and preferably0.03 to 2% by weight, based on the total weight of the composition. Thecouplers are also suitably present in amounts of 0.001 to 5% by weightand preferably 0.015 to 2% by weight. Their pH is preferably 7 to 11.5and can be adjusted thereto with the alkalising agents mentioned above.

The process for dyeing keratin fibres, in particular human hair,involving development with an oxidising agent consists in applying, tothe hair, the dyeing composition comprising both a dyestuff according tothe invention and dyestuff precursor, and in developing the colorationwith an oxidising agent, which is either present in the dyeingcomposition or is applied to the hair in a second step.

The oxidising agent is preferably hydrogen peroxide, urea peroxide or aper-salt. A solution of hydrogen peroxide of 20 volumes strength can beused in particular.

Once the composition has been applied to the keratin fibres with theoxidising agent, a period of 10 to 50 minutes, preferably 15 to 30minutes, is generally allowed, after which the keratin fibres arerinsed, optionally shampooed and rinsed again, and dried.

Of these compositions, the ones which are particularly preferred arethose which contain nitro dyestuffs of the formula (III) in which R'denotes alkoxyalkyl or a group of the formula: ##STR22## in which R₁ andR₂ and n have the meanings indicated above.

These compounds are new compounds and give rise to very luminous yellowcolorations which, when the compounds are used in compositions describedabove, have a good resistance to adverse weather conditions and washingand also a good degree of harmlessness.

The following Examples further illustrate the present invention.

PREPARATION EXAMPLE 1 Preparation of 2-N-butylamino-5-nitrophenol##STR23##

100 g (0.6 mol) of 3,4-methylenedioxynitrobenzene in 400 ml ofbutylamine are heated under reflux for 26 hours. The major part of thebutylamine is removed by distillation in vacuo and the residual productis treated with one litre of a 0.5N solution of hydrochloric acid. Thisgives a very thick gum which, after first being washed with a 0.5Nsolution of hydrochloric acid and then with water, is treated with oneliter of a normal solution of sodium hydroxide, with stirring. Theinsoluble fraction, which consists of the unreacted3,4-methylenedioxynitrobenzene, is filtered off. The filtrate containingsodium hydroxide is washed twice in succession by extraction with 300 mlof chloroform and then, after cooling to 0° C., it is neutralised byadding hydrochloric acid of density 1.18. The expected productprecipitates. It is filtered off, washed with water and then dried invacuo.

This gives 45 g of virtually pure 2-N-butylamino-4 -nitrophenolmonohydrate, which melts at 64° C.

After two recrystallisations from benzene and drying in vacuo at 80° C.for 8 hours, the product melts at 95° C. This is anhydrous2-N-butylamino-5-nitrophenol.

    ______________________________________                                                      Calculated for                                                  Analysis      C.sub.10 H.sub.14 N.sub.2 O.sub.3                                                         Found                                               ______________________________________                                        C %           57.14       57.23                                               H %           6.67        6.73                                                N %           13.38       13.42                                               O %           22.86       22.66                                               ______________________________________                                    

PREPARATION EXAMPLE 2 Preparation of2-N-(β-hydroxyethyl)-amino-5-nitrophenol ##STR24##

0.299 mol (50 g) of 3,4-methylenedioxynitrobenzene in 250 ml ofmonoethanolamine are heated in a boiling water-bath for 31/2 hours, withstirring. After the reaction medium has cooled, it is poured into 2liters of iced water to which 300 ml of hydrochloric acid of density1.18 have been added. The expected product precipitates. It is filteredoff, washed with water and then dissolved in 300 ml of a normal solutionof sodium hydroxide. By filtration of this sodium hydroxide solution, afew grams of initial product are removed. The filtrate is acidified topH 2 with a 5N solution of hydrochloric acid in order to precipitate the2-N-(β-hydoxyethyl)-amino-5-nitrophenol. The product is filtered off,washed with water and dried in vacuo. This gives 35 g of virtually pureproduct (melting point=207° C.). After recrystallisation from ethanol,the product melts at 208° C.

    ______________________________________                                                      Calculated for                                                  Analysis      C.sub.8 H.sub.10 N.sub.2 O.sub.4                                                          Found                                               ______________________________________                                        C %           48.48       48.39                                               H %           5.09        5.27                                                N %           14.14       14.32                                               ______________________________________                                    

PREPARATION EXAMPLE 3 Preparation of2-N-(β-diethylaminoethyl)-amino-5-nitrophenol ##STR25##

0.718 mol (120 g) of 3,4-methylenedioxynitrobenzene in 480 ml ofN,N-diethylethylenediamine are heated for 15 hours in a boilingwater-bath, with stirring. After the reaction mixture has cooled, it ispoured into 4,480 ml of iced water to which 1,330 ml of hydrochloricacid of density 1.18 have been added. The expected product crystallisesand is filtered off, washed carefully with a 2N solution of hydrochloricacid and then dried in vacuo.

This gives 135 g of virtually pure 2-N-(β-diethylaminoethyl)-amino-5-nitrophenol monohydrochloride monohydrate.

After two recrystallisations from water (7 ml per gram), the product isdried in vacuo.

It melts with decomposition at 221° C.

    ______________________________________                                                      Calculated for                                                  Analysis      C.sub.12 H.sub.22 N.sub.3 O.sub.4 Cl                                                      Found                                               ______________________________________                                        C %           46.83       46.48                                               H %           7.15        7.27                                                N %           13.66       13.66                                               O %           20.81       21.07                                               Cl %          11.55       11.46                                               ______________________________________                                    

PREPARATION EXAMPLE 4 Preparation of2-N-(β-aminoethyl)-amino-5-nitrophenol monohydrochloride monohydrate##STR26##

0.179 mol (30 g) of 3,4-methylenedioxynitrobenzene in 150 ml ofethylenediamine are heated in a boiling water-bath for one hour, withstirring. After the reaction medium has cooled, it is poured into 1,400ml of iced water to which 590 ml of hydrochloric acid of density 1.18have been added. The orange solution is kept at -10° C. for two days.The 2-N-(β-aminoethyl)-amino-5-nitrophenol monohydrochloride monohydratewhich has crystallised is filtered off and then washed with a 2Nsolution of hydrochloric acid and then with iced water. It is dried invacuo.

This gives 20 g of virtually pure product. melting point (withdecomposition)=253° C.

The product is recrystallised from water and then dried.

    ______________________________________                                                      Calculated for                                                  Analysis      C.sub.8 H.sub.14 N.sub.3 O.sub.4 Cl                                                       Found                                               ______________________________________                                        C %           38.17       38.16                                               H %           5.56         5.43                                               N %           16.70       16.94                                               O %           25.45       25.36                                               Cl %          14.11       14.27                                               ______________________________________                                    

PREPARATION EXAMPLE 5 Preparation of 2-amino-5-nitrophenol.

A solution of 0.18 mol (30 g) of 3,4-methylenedioxynitrobenzene in amixture of 240 ml of 28% strength ammonia solution and 240 ml ofdiethylene glycol dimethyl ether is heated at 100° C. for 28 hours in anautoclave. After cooling, 480 ml of water are added. The unreactedinitial product precipitates. It is recovered by filtration and thefiltrate is then neutralised with hydrochloric acid. After filtration,the filtrate is extracted with ethyl acetate. The ethyl acetate isdriven off in vacuo. The residue is treated with 25 ml of aceticanhydride and then kept in a boiling water-bath for 30 minutes. Aftercooling, the expected product is isolated in the form of the acetylderivative. This acetyl derivative is hydrolysed with 45 ml ofhydrochloric acid of density 1.17, at 90° C. for one hour. Afterdilution and neutralisation of the solution containing hydrochloricacid, 2-amino-5-nitrophenol is isolated by filtration. Meltingpoint=207° C.

PREPARATION EXAMPLE 6 Preparation of2-[2-hydroxy-3-N-(β-hydroxyethyl)-amino-6-nitrobenzyloxy]-ethylamine.##STR27##

The preparation of 2-N-(β-hydroxyethyl)-amino-5-nitrophenol has alreadybeen described in Example 2 above. During this preparation, afterheating 0.299 mol (50 g) of 3,4-methylenedioxynitrobenzene in 250 ml ofmonoethanolamine for 31/2 hours, the reaction medium is poured into 2liters of iced water to which 300 ml of hydrochloric acid of density1.18 have been added. The 2-N-(β-hydroxyethyl)-amino-5-nitrophenol isfiltered off and is purified by the process described. The melting pointis 207° C. and the yield 59%.

The mother liquors from filtration, cooled to 0° C., are renderedalkaline to pH 10 with a 5N solution of sodium hydroxide.

2-[2-Hydroxy-3-N-(β-hydroxyethyl)-amino-6-nitrobenzyloxy]-ethylamineprecipitates immediately and is filtered off, washed with water anddried. This gives 15 g of chromatographically pure product. The meltingpoint is 190° C.

    ______________________________________                                                      Calculated for                                                  Analysis      C.sub.11 H.sub.17 N.sub.3 O.sub.5                                                         Found                                               ______________________________________                                        C %           48.70       48.38                                               H %           6.32        6.35                                                N %           15.49       15.50                                               ______________________________________                                    

PREPARATION EXAMPLE 7 ##STR28## A. Preparation of2-N-(β-hydroxypropyl)-amino-5-nitrophenol

0.418 mol (70 g) of 3,4-methylenedioxynitrobenzene in 350 ml of1-aminopropan-2-ol are heated for 8 hours in a boiling-water bath andthe cooled reaction medium is then poured into 1,500 ml of iced water.About 5 g of unreacted initial product are removed by filtration.

The filtrate is treated with 330 ml of hydrochloric acid of density1.18, with stirring, so as to give a pH of 3.5. The expected productprecipitates in the form of crystals. It is filtered off, washed withwater and recrystallised from alcohol. After drying, 32 g of product areobtained. The melting point is 184° C. Yield: 36.3%.

    ______________________________________                                                      Calculated for                                                  Analysis      C.sub.9 H.sub.12 N.sub.2 O.sub.4                                                          Found                                               ______________________________________                                        C %           50.94       50.88                                               H %           5.70        5.69                                                N %           13.20       13.26                                               ______________________________________                                    

B. Preparation of2-[2-hydroxy-3-N-(β-hydroxypropyl)-amino-6-nitrobenzyloxy]-propylaminemonohydrate.

After the 2-N-(β-hydroxypropyl)-amino-5-nitrophenol phenol has beenfiltered off, the mother liquors, cooled to 0° C., are rendered alkalineto pH 10 with a 5N solution of sodium hydroxide and then saturated withsodium chloride, with stirring. The expected product precipitates. It isfiltered off, washed with water and redissolved in 140 ml of a 0.5Nsolution of hydrochloric acid for the purpose of purification. Afterfiltration to remove a small amount of insoluble material, this solutioncontaining hydrochloric acid is extracted twice with ethyl acetate inorder to remove a small amount of2-N-(β-hydroxypropyl)-amino-5-nitrophenol. It is then rendered alkalinewith ammonia solution. The expected product precipitates. It is filteredoff, washed with water and recrystallised twice from alcohol. Afterdrying in vacuo, it melts at 142° C.

    ______________________________________                                                     Calculated for                                                   Analysis     C.sub.13 H.sub.12 O.sub.5 N.sub.3.H.sub.2 O                                                Found                                               ______________________________________                                        C %          49.21        49.26                                               H %          7.25          7.22                                               N %          13.25        13.24                                               ______________________________________                                    

PREPARATION EXAMPLE 8 Preparation of2-N-(β,γ-dihydroxypropyl)amino-5-nitrophenol ##STR29## 10 g (0.0599 mol)of 3,4-methylenedioxynitrobenzene and 50 g (0.549 mol) of1-amino-2,3-propanediol in 25 ml of dimethylsulfoxide are heated toabout 100° C. for 101/2 hours. The reaction mixture is poured into 250 gof iced water. By filtration, 0.4 g of the starting nitro compound areremoved. The filtrate is acidified to pH 3 with 25 ml of 35% strengthhydrochloric acid and then treated with 100 g of sodium chloride beforebeing extracted with ethyl acetate. The extraction ethyl acetate isdriven off in vacuo. The residual oil (12 g) is fractionated bychromatography on silica gel 60 (MERCK). The purified expected productis eluted with a toluene/ethyl acetate (60/40) mixture. The solvent isdriven off in vacuo. The expected product crystallises and melts at 97°C. (6.7 g; yield=49%) EXAMPLE 1

The following dyeing composition is prepared:

    ______________________________________                                        2-N-(β-Diethylaminoethyl)-amino-5-nitrophenol                                                       0.25    g                                          monohydrochloride                                                             3-Nitro-4-N-(β-aminoethyl)-aminophenoxyethanol                                                      0.26    g                                          3-Nitro-4-N'-methylamino-N-(β-aminoethyl)-aniline                                                   0.38    g                                          dihydrobromide                                                                96° strength ethanol                                                                              10      g                                          Cemulsol NP.sub.4          12      g                                          Cemulsol NP.sub.9          15      g                                          Oxyethyleneated oleyl alcohol containing                                                                 1.5     g                                          2 mols of ethylene oxide                                                      Oxyethyleneated oleyl alcohol containing                                                                 1.5     g                                          4 mols of ethylene oxide                                                      20% strength aqueous solution of triethanol-                                                             0.5     g                                          amine                                                                         Water q.s.                 100     g                                          pH 7.5                                                                        ______________________________________                                    

When applied for 30 minutes at 28° C. to hair which has been bleachedwhite, this mixture imparts to the hair, after rinsing and shampooing, acopper-red coloration.

EXAMPLE 2

The following dyeing composition is prepared:

    ______________________________________                                        2-N-(β-Aminoethyl)-amino-5-nitrophenol                                                             0.215   g                                           monohydrochloride monohydrate                                                 2-N-(β-Hydroxyethyl)-amino-5-[4-N,N-di(β-                                                     0.2     g                                           hydroxyethyl)-aminoanilino]-1,4-benzoquinone                                  3-Nitro-4-N-(β-hydroxyethyl)-aminophenol                                                           0.105   g                                           3-Nitro-4-(β-hydroxyethyl)-aminophenyl                                                             0.2     g                                           β-hydroxypropyl ether                                                    2-Butoxyethanol           10      g                                           Cellosize WP03            2       g                                           Dimethyl-alkyl(copra)-hydroxyethylammonium                                                              2       g                                           chloride                                                                      20% strength aqueous solution of monoethanol-                                                           0.25    g                                           amine                                                                         Water q.s.                100     g                                           pH 8.5                                                                        ______________________________________                                    

When applied for 35 minutes at 30° C. to hair which has been bleachedstraw yellow, this mixture imparts to the hair, after rinsing andshampooing, an intense red coloration.

EXAMPLE 3

The following dyeing composition is prepared:

    ______________________________________                                        2-N-Butylamino-5-nitrophenol                                                                            0.205   g                                           2-Nitro-N-(β-aminoethyl)-aniline hydrochloride                                                     0.205   g                                           3-Nitro-4-amino-6-methyl-N-(β-aminoethyl)-                                                         0.4     g                                           aniline monohydrobromide monohydrate                                          Tetraaminoanthraquinone   0.31    g                                           Carboxymethylcellulose    2       g                                           2-Butoxyethanol           10      g                                           Ammonium lauryl-sulphate  5       g                                           5% strength ammonia solution                                                                            1       g                                           Water q.s.                100     g                                           ______________________________________                                    

When applied for 20 minutes at 30° C. to hair which has been bleachedwhite, this mixture imparts to the hair, after rinsing and shampooing, acoppery chestnut coloration.

EXAMPLE 4

The following dyeing composition is prepared:

    ______________________________________                                        2-N-Butylamino-5-nitrophenol                                                                             1.5    g                                           3-Nitro-4-N-(β-hydroxyethyl)-aminophenol                                                            0.2    g                                           3-Nitro-4-N'-methylamino-N,N-di-(β-hydroxy-                                                         0.51   g                                           ethyl)-aniline                                                                2-Butoxyethanol            10     g                                           Cemulsol NP4               12     g                                           Cemulsol NP9               15     g                                           Oxyethyleneated oleyl alcohol containing                                                                 1.5    g                                           2 mols of ethylene oxide                                                      Oxyethyleneated oleyl alcohol containing                                                                 1.5    g                                           4 mols of ethylene oxide                                                      20% strength aqueous solution of triethanolamine                                                         0.15   g                                           Water q.s.                 100    g                                           pH 8.5                                                                        ______________________________________                                    

When applied for 20 minutes at 30° C. to hair which has been bleachedwhite, this mixture imparts to the hair, after rinsing and shampooing, acoppery blond coloration.

EXAMPLE 5

The following dyeing composition is prepared:

    ______________________________________                                        2-N-(β-Aminoethyl)-amino-5-nitrophenol                                                               0.03   g                                          monohydrochloride monohydrate                                                 2-N-(β-Hydroxyethyl)-amino-5-nitrophenol                                                             0.15   g                                          3-Nitro-4-amino-6-methyl-N-(β-hydroxyethyl)-aniline                                                  0.07   g                                          3-Nitro-4-N'-methylamino-N,N-di-(β-hydroxy-                                                          0.15   g                                          ethyl)-aniline                                                                2-Butoxyethanol             10     g                                          Lauramide                   1.5    g                                          Hydroxyethylcellulose       5      g                                          Lauric acid                 1      g                                          Monoethanolamine            2      g                                          Water q.s.                  100    g                                          pH 10                                                                         ______________________________________                                    

When applied for 20 minutes at 30° C. to hair which has been bleachedwhite, this mixture imparts to the hair, after rising and shampooing, alight mahogany coloration.

EXAMPLE 6

The following dyeing composition is prepared:

    ______________________________________                                        2-N-(β-Diethylaminoethyl)-amino-5-nitrophenol                                                        0.1    g                                          monohydrochloride                                                             3-Nitro-4-aminophenol       0.09   g                                          3-Nitro-4-N'-methylamino-N,N-di-(β-hydroxy-                                                          0.17   g                                          ethyl)-aniline                                                                3-Nitro-4-amino-6-methyl-N-(β-hydroxyethyl)-aniline                                                  0.05   g                                          2-Butoxyethanol             10     g                                          Cellosize WP 03             2      g                                          Dimethyl-alkyl(copra)-hydroxyethylammonium                                                                2      g                                          chloride                                                                      20% strength by weight aqueous solution of                                                                0.5    g                                          monoethanolamine                                                              Water q.s.                  100    g                                          pH 8.7                                                                        ______________________________________                                    

When applied for 30 minutes at 30° C. to hair which has been bleachedstraw yellow, this mixture imparts to the hair, after rinsing andshampooing, a coppery chestnut coloration.

The examples which follow are intended to illustrate other compositionsaccording to the invention. In these examples, the colorations obtainedare expressed by the Munsell notations, after an application time of 30minutes at 30° C.

EXAMPLE 7

    ______________________________________                                        2-N-Butylamino-5-nitrophenol                                                                             0.8     g                                          96° strength ethanol                                                                              10      g                                          Alfol C.sub.16/18          8       g                                          Lanette wax E              0.5     g                                          Cemulsol B                 1       g                                          Oleic diethanolamide       1.5     g                                          20% strength aqueous solution of triethanolamine                                                         1       g                                          Water q.s.                 100     g                                          pH = 8                                                                        On bleached hair: 4 Y 8/9                                                     on 90% naturally white hair: 4.5 Y 6/7.                                       ______________________________________                                    

EXAMPLE 8

    ______________________________________                                        2-N-(β-Aminoethyl)-amino-5-nitrophenol                                                               1.2    g                                          monohydrochloride monohydrate                                                 96° strength ethanol 10     g                                          Hydroxyethylcellulose       2      g                                          Dimethyl-alkyl(copra)-hydroxyethylammonium                                                                2      g                                          chloride                                                                      20% strength aqueous solution of monoethanolamine                                                         1      g                                          Water q.s.                  100    g                                          pH 6                                                                          on bleached hair: 3 Y 8/12                                                    on 90% naturally white hair: 3.5 Y 6.5/8.                                     ______________________________________                                    

EXAMPLE 9

    ______________________________________                                        2-N-(β-Aminoethyl)-amino-5-nitrophenol                                                             0.04   g                                            monohydrochloride monohydrate                                                 Diethanolamides of copra fatty acids                                                                    2.2    g                                            Lauric acid               0.8    g                                            96° strength ethanol                                                                             5      g                                            Ethylene glycol monoethyl ether                                                                         2      g                                            Monoethanolamine          1      g                                            Water q.s.                100    g                                            pH 6.7                                                                        On bleached hair: 4.5 Y 8/6                                                   ______________________________________                                    

EXAMPLE 10

    ______________________________________                                        2-N-(β-Diethylaminoethyl)-amino-5-nitrophenol                                                      1.96    g                                           monohydrochloride                                                             96° strength ethanol                                                                             10      g                                           Carbopol 934              2       g                                           22° B strength ammonia solution                                                                  3       g                                           Water q.s.                100     g                                           pH 9                                                                          On bleached hair: 2.5 Y 8/12                                                  On 90% naturally white hair: 4 y 6/8                                          ______________________________________                                    

EXAMPLE 11

The following dyeing composition is prepared:

    ______________________________________                                        2-N-(β-Hydroxypropyl)-amino-5-nitrophenol                                                          0.6    g                                            2-Butoxyethanol           10     g                                            Alfol C.sub.16 /C.sub.18  8      g                                            Lanette wax E             0.5    g                                            Cemulsol B                1      g                                            Oleic diethanolamide      1.5    g                                            5% strength ammonia solution                                                                            1      g                                            Water q.s.                100    g                                            pH 8.8                                                                        ______________________________________                                    

When applied to bleached hair for 30 minutes at 30° C., this mixtureimparts to the hair, after rinsing and shampooing, a coloration of 5 Y7/10 according to the Munsell notation.

EXAMPLE 12

The following dyeing composition is prepared:

    ______________________________________                                        2-N-(β-Hydroxypropyl)-amino-5-nitrophenol                                                            0.2    g                                          Tetraaminoanthraquinone     0.35   g                                          3-Nitro-4-N-(β-hydroxyethyl)-aminophenol                                                             0.1    g                                          3-Nitro-4-amino-6-methyl-N-(β-hydroxyethyl)-                                                         0.05   g                                          Propylene glycol            10     g                                          Cellosize WP 03             2      g                                          Cetyldimethylhydroxyethylammonium chloride                                                                2      g                                          20% strength solution of triethanolamine                                                                  1      g                                          Water q.s.                  100    g                                          pH 8.2                                                                        ______________________________________                                    

When applied to bleached hair for 20 minutes at 30° C., this mixtureimparts to the hair, after rinsing and shampooing, a coppery blondcoloration.

EXAMPLE 13

The following dyeing composition is prepared:

    ______________________________________                                        2-[2-Hydroxy-3-N-(β-hydroxypropyl)-amino-6-                                                         0.45   g                                           nitrobenzyloxy]-propylamine                                                   Propylene glycol           10     g                                           Carbopol 934               2      g                                           5% strength ammonia solution                                                                             3      g                                           Water q.s.                 100    g                                           pH 5.2                                                                        ______________________________________                                    

When applied to bleached hair for 30 minutes at 30° C., this mixtureimparts to the hair, after rinsing and shampooing, a coloration of 1.5 Y7/10 according to the Munsell notation.

EXAMPLE 14

The following dyeing composition is prepared:

    ______________________________________                                        2-[2-Hydroxy-3-N-(β-hydroxypropyl)-amino-6-                                                         0.45   g                                           nitrobenzyloxy]-propylamine                                                   Propylene glycol           10     g                                           Carbopol 934               2      g                                           20% strength solution of monoethanolamine                                                                7      g                                           Water q.s.                 100    g                                           pH 7.7.                                                                       ______________________________________                                    

When applied to bleached hair for 20 minutes at 28° C., this mixtureimparts to the hair, after rinsing and shampooing, a coloration of 5 YR6/11 according to the Munsell notation.

EXAMPLE 15

The following dyeing composition is prepared:

    ______________________________________                                        2-[2-Hydroxy-3-N-(β-hydroxypropyl)-amino-6-                                                         0.15   g                                           nitrobenzyloxy]-propylamine                                                   2-N-(β-Hydroxyethyl)-amino-5-[4-N,N-di-(β-                                                     0.15   g                                           hydroxyethyl)-aminoanilino]-1,4-benzoquinone                                  3-Nitro-4-amino-N-(β-hydroxyethyl)-aniline                                                          0.13   g                                           3-Nitro-4-N'-(β-aminoethyl)-amino-N,N-di-(β-                                                   0.03   g                                           hydroxyethyl)-aniline hydrochloride                                           96° strength ethanol                                                                              5      g                                           Diethanolamides of copra fatty acids                                                                     2.2    g                                           Lauric acid                0.8    g                                           Ethylene glycol monoethyl ether                                                                          2      g                                           20% strength solution of monoethanolamine                                                                1      g                                           Water q.s.                 100    g                                           pH 8.4                                                                        ______________________________________                                    

When applied to bleached hair for 25 minutes at 30° C., this mixtureimparts to the hair, after rinsing and shampooing, a copper colorationwith a purple sheen.

EXAMPLE 16

The following dyeing composition is prepared:

    ______________________________________                                        2-[2-Hydroxy-3-N-(β-hydroxyethyl)-amino-6-                                                         0.54   g                                            nitrobenzyloxy]-ethylamine                                                    10% strength solution of lactic acid                                                                    0.5    g                                            Carboxymethylcellulose    2      g                                            Ammonium lauryl-sulphate  5      g                                            2-Butoxyethanol           10     g                                            Water q.s.                100    g                                            pH 6.2                                                                        ______________________________________                                    

When applied to bleached hair for 20 minutes at 30° C., this mixtureimparts to the hair, after rinsing and shampooing, a coloration of 7.5YR 6/10 according to the Munsell notation.

EXAMPLE 17

The following dyeing composition is prepared:

    ______________________________________                                        2-[2-Hydroxy-3-N-(β-hydroxyethyl)-amino-6-                                                          0.25   g                                           nitrobenzyloxy]-ethylamine                                                    3-Nitro-4-N'-(β-aminoethyl)-amino-N,N-di-(β-                                                   0.095  g                                           hydroxyethyl)-aniline hydrochloride                                           2-Methyl-4-amino-5-nitrophenol                                                                           0.065  g                                           2-Butoxyethanol            10     g                                           Water q.s.                 100    g                                           pH 6.25                                                                       ______________________________________                                    

When applied to 95% naturally white hair for 25 minutes at 28° C., thismixture imparts to the hair, after rinsing and shampooing, a copperylight blond coloration.

The reference examples which follow are intended to illustrate thepreparation of the 3-nitro-4-N-(β-aminoethyl)-aminophenoxyethanol usedin Example 1 and the preparation of the3-nitro-4-(β-hydroxyethyl)-aminophenyl β-hydroxypropyl ether used inExample 2.

EXAMPLE 18

The following dyeing composition is prepared:

    ______________________________________                                        2-N-(β,γ-dihydroxypropyl)amino-5-nitropenol                                                  3       g                                           96° strength ethanol                                                                             10      g                                           Cellosize WP 03           2       g                                           5% strength ammonia solution                                                                            1.5     g                                           Water qs                  100     g                                           pH 8.20                                                                       ______________________________________                                    

When applied for 20 minutes at 20° C. to hair which has been bleached towhite, this mixture impacts to the hair, after rinsing and shampooing, avery intense orange coloration.

EXAMPLE 19

The following dyeing composition is prepared:

    ______________________________________                                        2-N-(β,γ-dihydroxypropyl)amino-5-nitriophenol                                                 0.4    g                                           paraphenylenediamine       0.265  g                                           paraaminophenol            0.4    g                                           2,4-diaminophenoxyethanol dihydrochloride                                                                0.105  g                                           resorcinol                 0.25   g                                           metaaminophenol            0.21   g                                           2-methyl-5-N-(β-hydroxyethyl)aminophenol                                                            0.15   g                                           Cemulsol NP4               21     g                                           Cemulsol NP 9              24     g                                           Oleic acid                 4      g                                           2-butoxyethanol            3      g                                           96° strength ethanol                                                                              10     g                                           Masquol DTPA (sodium salt of diethylenetriamine                                                          2.5    g                                           pentaacetic acid)                                                             35° B strength sodium bisulphite solution                                                         1      g                                           22° B strength ammonia solution                                                                   10     g                                           water q.s.                 100    g                                           pH = 10.3                                                                     ______________________________________                                    

100 g of hydrogen peroxide of 20 volumes strength are added at the timeof application.

When applied for 20 minutes at 28° C. to hair which has been bleached towhite, this mixture imparts to the hair, after rinsing and shampooing, agolden chestnut coloration.

EXAMPLE 20

The following dyeing composition is prepared:

    ______________________________________                                        2-N-(β,γ-dihydroxypropyl)amino-5-nitrophenol                                                   0.42   g                                          1-N-(β-aminoethyl)amino-2-nitro-4-N',N'-                                                             0.265  g                                          di(β-hydroxyethyl)aminobenzene                                           1-amino-2-nitro-4-N-(β-hydroxyethyl)                                                                 0.31   g                                          amino-5-methylbenzene                                                         Carbopol 934                2      g                                          Monoethanolamine (20% strength aqueous solution)                                                          10     g                                          Water qs                    100    g                                          pH: 8                                                                         ______________________________________                                    

When applied for 25 minutes at 28° C. to 90% naturally white hair, thismixture imparts to the hair, after rinsing and shampooing, a coppercoloration.

REFERENCE EXAMPLE 1 Preparation of3-nitro-4-(β-aminoethyl)-aminophenoxyethanol ##STR30## 1st step:Preparation of 3-nitro-4-chlorophenoxyethanol.

2.5 mols (434 g) of 4-chloro-3-nitrophenol are dissolved in 1,300 ml ofdimethylformamide heated to 70° C. beforehand. 3 mols of powderedpotassium hydroxide (210 g of 80% pure potassium hydroxide) are added tothis solution and 3 mols (534 g) of glycol bromohydrin are thenintroduced in the course of 30 minutes, with stirring, whilst keepingthe temperature at 70° C. When the addition has ended, the reactionmedium is kept at 70° C. for 1 hour. 1 mol of powdered potassiumhydroxide (70 g of 80% pure potassium hydroxide) and 1 mol of glycolbromohydrin (178 g) are then added. After heating for 1 hour, a further1 mol of potassium hydroxide and 1 mol of glycol bromohydrin are added.The heating is continued for a further 1 hour and the cooled reactionmedium is then poured into 7.5 liters of iced water. The expectedproduct precipitates. It is filtered off and washed carefully with a 3Nsolution of sodium hydroxide and then with water. After drying in vacuo,it melts at 96° C.

2nd step: Preparation of 3-nitro-4-(β-aminoethyl)-aminophenoxyethanol.

0.4 mol (87 g) of 3-nitro-4-chlorophenoxyethanol in 225 ml ofethylenediamine are heated under reflux for 1 hour. The cooled reactionmedium is poured into 500 g of iced water. The solution is renderedalkaline to pH 10 with a 10N solution of sodium hydroxide. The expectedproduct crystallises. It is filtered off, washed with cold water anddried in vacuo at 50° C. It melts at 110° C. After recrystallisationfrom ethanol, it melts at 112°C.

    ______________________________________                                                      Calculated for                                                  Analysis      C.sub.10 H.sub.15 N.sub.3 O.sub.4                                                         Found                                               ______________________________________                                        C %           49.78       49.86                                               H %           6.27        6.32                                                N %           17.42       17.35                                               O %           26.53       26.41                                               ______________________________________                                    

REFERENCE EXAMPLE 2 Preparation of3-nitro-4-N-(β-hydroxyethyl)-aminophenyl β-hydroxypropyl ether.##STR31##

A solution of 0.2 mol (39.6 g) of3-nitro-4-N-(β-hydroxyethyl)-aminophenol in 104 ml of a 2.3N solution ofsodium hydroxide (0.24 mol) is heated beforehand to about 100° C. and0.24 mol (22.7 g) of 1-chloropropan-2-ol is then added thereto. Afterthe reaction medium has been kept in a boiling water-bath for 2 hours,it is and with 0.12 mol (11.34 g) of 1-chloropropan-2-ol. The heating ismaintained for a further 2 hours in the boiling water-bath. Aftercooling to 0° C., the medium is rendered alkaline to pH 9 with asolution of sodium hydroxide. The expected product crystallises and itis filtered off and washed with a normal solution of sodium hydroxideand then with water. After drying in vacuo at 60° C., it melts at 118°C. After recrystallisation from ethanol and recrystallisation from ethylacetate, it melts at 122° C.

    ______________________________________                                                      Calculated for                                                  Analysis      C.sub.11 H.sub.16 N.sub.2 O.sub.5                                                         Found                                               ______________________________________                                        C %           51.56       51.73                                               H %           6.29        6.24                                                N %           10.93       10.82                                               O %           31.22       31.15                                               ______________________________________                                    

In the preceding examples, the tradenames used denote the followingproducts:

Cemulsol NP4: Nonylphenol containing 4 mols of ethylene oxide, sold byRhone Poulenc.

Cemulsol NP9: Nonylphenol containing 9 mols of ethylene oxide, sold byRhone, Poulenc.

Cellosize WPO3: Hydroxyethylcellulose sold by Union Carbide.

Lauramide: Lauric acid monoethanolamide sold by Witco.

Alfol C₁₆ /₁₈ : Cetyl/stearyl alcohol sold by Condea.

Lanette wax E: Partially sulphated cetyl/stearyl alcohol sold by Henkel.

Cemulsol B: Oxyethyleneated castor oil sold by Rhone Poulenc.

Carbopol 934: Acrylic acid polymer with a molecular weight of 2 to 3million, sold by Goodrich Chem. Company.

Trilon B: Ethylenediaminetetraacetic acid.

We claim:
 1. Process for the preparation of a nitroaniline whichcomprises reacting a compound of the formula RNH₂ with3,4-methylenedioxynitrobenzene to produce a product of the formula:##STR32## or a salt thereof, in which R denotes hydrogen, alkyl,monohydroxyalkyl or polyhydroxyalkyl, alkoxyalkyl, or aminoalkyl of theformula: ##STR33## in which R₁ and R₂, which are identical or different,denote hydrogen, alkyl or monohydroxyalkyl or polyhydroxyalkyl and ndenotes an integer from 2 to
 4. 2. Process according to claim 1 in which3,4-methylenedioxynitrobenzene is heated in an excess of amine of theformula RNH₂, at a temperature of 70° to 170° C., for 1 to 30 hours. 3.Process according to claim 1 in which R denotes alkyl, monohydroxyalkylor polyhydroxyalkyl or alkoxyalkyl and a dilute solution of hydrochloricacid is added to the crude reaction product, the product insoluble inthe hydrochloric acid medium is isolated, and, after washing with water,is treated with a dilute solution of sodium hydroxide, the resultingmixture is filtered and the product isolated after acidification of thefiltrate.
 4. Process according to claim 1 in which R denotes ##STR34##and the crude reaction product is taken up in a 2 to 3N solution ofhydrochloric acid, the product crystallising in the form of thehydrochloride after cooling.
 5. Process according to claim 1 in which anamine of the formula R₁ NH₂, in which R₁ denotes --CH₂ CH₂ OH or --CH₂CHOHCH₃, is reacted with 3,4-methylenedioxynitrobenzene using an excessof amine of the formula R₁ NH₂, at a temperature of 70° to 170° C., for1 to 30 hours, a dilute solution of hydrochloric acid is added to thecrude reaction product obtained, the product insoluble in thehydrochloric acid medium is filtered off to give a compound of theformula: ##STR35## the mother liquors resulting from the filtration arerendered alkaline with a solution of sodium hydroxide so as toprecipitate a product of the formula: ##STR36## in which A denotes--OCH₂ CH₂ or ##STR37## the product thus obtained being purified. 6.Process according to claim 1 in which R denotes methyl, ethyl, propyl,n-butyl, β-hydroxyethyl, β-aminoethyl or diethylaminoethyl.
 7. A processfor the preparation of nitroaniline which comprises heating3,4-methylenedioxynitrobenzene with an excess of an amine of the formulaRNH₂, at a temperature of 70° to 170° C., for 1 to 30 hours to produce aproduct of the formula: ##STR38## or a salt thereof, in which R denoteshydrogen, alkyl, monohydroxyalkyl or polyhydroxyalkyl, alkxoyalkyl, oraminoalkyl of the formula: ##STR39## in which R₁ and R₂, which areidentical or different, denote hydrogen, aklyl or monohydroxyalkyl orpolyhydroxyalkyl and n denotes an integer from 2 to
 4. 8. A process forthe preparation of nitroaniline which comprises heating in the presenceof only non-polar solvents, 3,4-methylenedioxynitrobenzene with anexcess of an amine of the formula RNH₂, at a temperature of 70° to 170°C., for 1 to 30 hours to produce a product of the formula: ##STR40## ora salt thereof, in which R denotes hydrogen, alkyl, monohydroxyalkyl orpolyhydroxyalkyl, alkoxyalkyl, or aminoalkyl of the formula: ##STR41##in which R₁ and R₂, which are identical or different, denote hydrogen,alkyl or monohydroxyalkyl or polyhydroxyalkyl and n denotes an integerfrom 2 to 4.